OPEN The Non-innocent Phenalenyl Unit: An SUBJECT AREAS: Electronic Nest to Modulate the Catalytic CATALYSIS HOMOGENEOUS CATALYSIS Activity in Hydroamination Reaction CHEMISTRY Arup Mukherjee, Tamal K. Sen, Pradip Kr Ghorai & Swadhin K. Mandal ORGANOMETALLIC CHEMISTRY Department of Chemical Sciences, Indian Institute of Science Education and Research-Kolkata, Mohanpur-741252, India. Received 4 April 2013 The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, Accepted material chemistry to device physics acting as key electronic reservoir which has not only led to the best 9 September 2013 organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a Published homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl 2 October 2013 unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which Correspondence and in turn determines the outcome of the catalysis. requests for materials should be addressed to 1 S.K.M. (swadhin. on-innocent ligands (NILs) have long attracted attention because of their unusual redox properties and [email protected]. their apparent, often deceptive, ability to stabilize metals in unusual oxidation states. The NILs have been employed not only for spectroscopic studies2,3 but also in different chemical transformations4,5. It may be in) N postulated that due to the presence of easily accessible frontier orbitals in the NILs as compared to those of typical ligands, they facilitate electronic transfer through an inverted bonding process6. These ligands are now emerging as synthetically useful and attractive scaffolds with broad and exciting perspectives7. Nevertheless, fully exploring the potential of these NILs in group–transfer chemistry, energy storage and conversion, biological applications still remains in its early stage and in particular the influence of NILs in a catalytic reaction has remained in its infancy8,9. Though the area is dominated by coordination chemists10 and spectroscopists looking at influence of NIL in metals oxidation state, this concept is gradually entering into the area of catalysis8. In particular, in the field of organometallic chemistry, the NILs are emerging with ample opportunities in the realm of catalysis5. In this context, recently we introduced phenalenyl (PLY) unit as a potential ligand backbone to study their influence on the catalytic activity in ring opening polymerization (ROP) reactions11. Phenalenyl is a well-known odd alternant hydrocarbon with three fused benzene rings12 with ability to form three redox species: cation, radical, and anion (Figure 1a) using its readily avaialable nonbonding orbital (NBO)13. The concept of designing neutral free radical based conductors using this nonbonding orbital of phenalenyl was first proposed by Haddon14–17. Subsequently, this idea led to the discovery of the best neutral organic conductor at room temper- ature15. Recent articles by Morita, Takui and Hicks described the present status of phenalenyl based material chemistry emphasizing the radical electronic state of phenalenyl molecule12,18. On the other hand, we posed a question whether the presence of the readily available nonbonding orbital in the cationic state of phenalenyl unit19 (State 1, Figure 1a) can be utilized to design well-defined molecular catalysts which will influence the catalytic activity in a homogeneous organic transformation. It was postulated that on coordination to a metal ion, the phenalenyl unit will generate the closed shell cationic state and the empty NBO will function as electron acceptor. Recently, we have shown that the cationic state of phenalenyl unit when created with zinc metal coordination can be used as non-innocent building block for construction of spin memory device which functions based on the ability of electron acceptance of the phenalenyl unit20. In this study, we have chosen a homogeneous catalytic process, namely guanylation or hydroamination of carbodiimides with aromatic amines. Earlier study suggests that the hydroamination of carbodiimide proceeds via the methane liberation and formation of the metal-amide complex. The reaction proceeds via a transition state formed by interaction of amine and catalyst, presumably involving the transfer of electron density from amine to catalyst21. We became interested to study this particular homogeneous process to unravel the exact role of SCIENTIFIC REPORTS | 3 : 2821 | DOI: 10.1038/srep02821 1 www.nature.com/scientificreports (a) + Energy CationRadical Anion State 1 State 2 State 3 (Closed shell) (Open shell) (Closed shell) (b) + + + + + O O N O N O N N N N Al- Al- Cy Al- Al- Cy Al- Cy Me Me Me Me Me Me Me Me Me Me 1 2 3 4 5 Figure 1 | (a) The three redox species of phenalenyl moiety: cation when the NBO is empty, radical when the NBO is singly occupied, and anion when the NBO is completely filled19; (b) Organoaluminum complexes (1–5) based on phenalenyl ligand. non-innocent behavior of phenalenyl ligand in the catalytic outcome; complexes, 3 and 5 were accomplished by reacting [HN(Cy),O–PLY] since the influence of the NIL in catalytic reaction is not very well and [HN(Cy),N(Cy)–PLY] ligands, respectively with AlMe3 under the understood8. The catalytic addition of amine to carbodiimides (also evolution of methane (Figure 2). Asolutionof[HN(Cy),O–PLY]or known as guanylation or hydroamination) offers an efficient and atom- [HN(Cy),N(Cy)–PLY]ligandintoluenewasaddeddrop-by-dropto economical route to produce substituted guanidines, which is of great the solution of AlMe3 in toluene in a 151.2 stoichiometric ratio at interest to academic and industrial researchers22.Asapartofour 278uCandfinallyheatedat90uC or at 110uCfor6hor24hto ongoing interest in the development of catalytic systems for hydroa- yield the complex 3 or 5 (Figure 2). Absence of any characteristic 23–25 1 mination reaction , herein we report the catalytic activity of a series N–H resonance at d 12.5 or 14.0 ppm in C6D6 as revealed by the H of phenalenyl ligand based organoaluminum complexes towards NMR spectrum of the reaction mixture establishes almost quantitative hydroamination of carbodiimides. In the present study, five organoa- conversion of the reactants into products in case of 3 and 5.Both luminum complexes, namely [(O,O–PLY)]AlMe2 (1), [N(Me),O–PLY] complexes 3 and 5 were characterized by 1HNMR,13CNMR AlMe2 (2), [N(Cy),O–PLY]AlMe2 (3), [N(Me),N(Me)–PLY]AlMe2 spectroscopy, elemental analysis and single crystal X-ray diffraction (4), and [N(Cy),N(Cy)–PLY]AlMe (5)(Figure1b)wereusedfor 1 2 studies. H NMR spectra of 3 and 5 in C6D6 exhibitasingletatd catalytic hydroamination of carbodiimides to primary aromatic 0.01 and 20.10 ppm, respectively attributing to the proton resonance amines. arising from the methyl group bound to the aluminum ion. The 13C NMR spectra of 3 and 5 in C6D6 exhibitasingletatd 24.5 and Results 23.5 ppm, respectively assigned to the 13C resonance arising from Syntheses and characterization. This study utilized organoaluminum the methyl group bound to the aluminum ion. The structures of complexes of phenalenyl ligands based on O,O– (HO,O–PLY), complexes 3 and 5 were determined unambiguously by single crystal N,O– [HN(Me),O–PLY and HN(Cy),O–PLY)] and N,N– [HN(Me), X-ray diffraction technique (Figure 2). Suitable crystals of 3 and 5 were N(Me)–PLY and HN(Cy),N(Cy)–PLY] donor combinations. The obtained from cold toluene solution at 220uC and 0uC, respectively. organoaluminum complexes 1, 2, and 4 were synthesized according Complexes 3 and 5 were crystallized in the monoclinic and triclinic to the literature procedure11. Synthesis of the new organoaluminum space group C2/c and P ¯ı, respectively with one molecule in the SCIENTIFIC REPORTS | 3 : 2821 | DOI: 10.1038/srep02821 2 www.nature.com/scientificreports Figure 2 | Syntheses and molecular structures of the organoaluminum complexes 3 and 5 bearing phenalenyl ligands as determined by single crystal X-ray diffraction studies. Thermal ellipsoids are drawn with 50% probability level. Selected bond distances (A˚ ) and angles (u) of (a) 3: Al(1)–N(1) 1.9429 (15), Al(1)–O(1) 1.7820 (13), Al(1)–C(20) 1.9590 (19), Al(1)–C(21) 1.9659 (18), N(1)–C(13) 1.335 (2), O(1)–C(3) 1.3071 (19); N(1)–Al(1)–O(1) 95.19(6), N(1)–Al(1)–C(20) 112.02(7), O(1)–Al(1)–C(21) 107.30(7), C(20)–Al(1)–C(21)115.19(8); (b) 5: Al(1)–N(1), 1.900(2)), Al(1)–N(2) 1.899(2), Al(1)– C(22), 1.981(3), AI(1)–C(23), 1.976(3), N(2)–AI(1) 1.896(9), N(1)–AI(1) 1.918(9), N(1)–Al(1)–N(2) 97.5(6), N(1)–Al(1)–C(27) 109.7(9), N(2)– Al(1)–C(26) 107.9(9), C(27)–Al(1)–C(26) 115.4(9). asymmetric unit in both the cases. The X-ray structures of 3 and 5 guanidine (7) within 30 h at 25uC (Table 1, entry 2). Subsequently, reveal a distorted tetrahedral geometry around the aluminium ion. The the amount of catalyst loading was varied to see the most effective observed Al–C bond distances in 3 are Al(1)–C(20), 1.9590 (19) A˚ and catalytic condition. It was found that 5 mol% of catalyst loading Al(1)–C(21) 1.9659(18) A˚.